CN103240127A - Thermo-sensitive type hydrogel loaded tungsten catalyst and preparation method thereof - Google Patents
Thermo-sensitive type hydrogel loaded tungsten catalyst and preparation method thereof Download PDFInfo
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- CN103240127A CN103240127A CN 201310188394 CN201310188394A CN103240127A CN 103240127 A CN103240127 A CN 103240127A CN 201310188394 CN201310188394 CN 201310188394 CN 201310188394 A CN201310188394 A CN 201310188394A CN 103240127 A CN103240127 A CN 103240127A
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Abstract
The invention provides a thermo-sensitive type hydrogel loaded tungsten catalyst and a preparation method thereof. The preparation method comprises the following steps of: at room temperature, respectively weighing a certain quantity of a thermo-sensitive type monomer, a cationic monomer and a functional monomer, dissolving the monomers into a certain quantity of water under stirring so as to prepare a monomer solution of certain concentration, adding a certain quantity of an initiator and a cross-linking agent into the solution, stirring so as to obtain a mixed solution, putting the mixed solution into a water-bath pot of a certain temperature, reacting for a certain time so as to obtain a product, soaking the product in water for 48h at room temperature, and finally drying so as to obtain dry gel; soaking a certain quantity of the dry gel into a tungsten-containing compound solution of certain concentration, continuously stirring for hours at room temperature, and standing for 1 day; and washing the product with water for multiple times so as to obtain a white solid, and drying the solid at 80 DEG C till being in constant weight, so as to obtain the thermo-sensitive type hydrogel loaded tungsten catalyst. The preparation method is simple to operate and free of environmental pollution; and the prepared catalyst is stable in structure, the activity of catalyzing synthesis of adipic acid is high, and the yield can be 80%.
Description
Technical field
The present invention relates to temperature-sensitive hydrogel load tungsten catalyst and preparation method thereof, relate in particular to a kind of heterogeneous catalytic oxidation synthesizing adipic acid catalyst, belong to catalytic field.
Background technology
Adipic acid is important organic intermediate, and its industrial preparative method mainly adopts nitric acid oxidation method.This method is owing to use the red fuming nitric acid (RFNA) of strong oxidizing property, and equipment corrosion is serious, and the NxO that produces is considered to cause one of reason that global warming and ozone reduce, and causes great pollution to environment.Because more and more higher to environmental requirement, green synthesizing adipic acid receives much concern;
The catalytic oxidation system that the more green synthesizing adipic acid system of present research is Tungstenic compound-hydrogen peroxide, yet there is the two-phase problem under study for action, the substrate organic phase is fully contacted with catalyst with the oxidant of aqueous phase, thereby guarantee that oxidation reaction carries out smoothly.For head it off, have and use surfactant as consisting of phase-transferring agent, as: trioctylphosphine methylsulfuric acid hydrogen ammonium with contain the primary amine of long carbochain or the sulfate of tertiary amine.The surfactant type of use catalyst is also arranged, and this catalyst contains lipophilic group and hydrophilic radical, both can play the role of phase transfer, can play catalytic action again.Also have by forming the two-phase problem that microemulsion improves reaction.Yet in the conventional method, or consisting of phase-transferring agent costliness or synthetic catalyst are complicated, or catalyst need recycle by concentrating, and process is complicated;
Therefore develop a kind of two-phase catalyst of tungstenic and adopt better simply preparation method most important.
Summary of the invention
The invention provides a kind of temperature-sensitive hydrogel load tungsten catalyst and preparation method thereof, cost of material is cheap, and the preparation process environmental pollution is little, the gained catalyst is stable, have advantages of high catalytic activity, under the lower situation of use amount, can obtain higher adipic acid yield;
One of purpose of the present invention is to provide a kind of catalyst with synthesizing adipic acid of high catalytic activity;
Another object of the present invention provides above-mentioned Preparation of catalysts method;
The present invention adopts following technical scheme:
(1) under the room temperature, takes by weighing temperature sensitive type monomer, cationic monomer and the function monomer of certain mass respectively, be dissolved in a certain amount of water under stirring and make certain density monomer solution;
(2) in above-mentioned solution, add a certain amount of initator and crosslinking agent, obtain mixed solution after the stirring;
(3) obtain product after above-mentioned mixed solution being placed the water-bath reaction certain hour of uniform temperature;
(4) above-mentioned product at room temperature is soaked in water 48 h repeatedly change water to remove unreacted monomer and soluble polymer, and oven dry at last obtains xerogel;
(5) soak a certain amount of xerogel with certain density Tungstenic compound solution, at room temperature continuous stirring a few hours, leave standstill 1d then.Product repeatedly wash white solid, under 80 ℃, dry to constant weight, namely obtain hydrogel load tungsten catalyst;
(6) by following scheme the hydrogel load tungsten catalyst for preparing is carried out catalytic oxidation synthesizing adipic acid performance evaluation:
In 50 ml flasks, add a certain amount of catalyst, 11 ml 30%H
2O
2, 0.31 g oxalic acid, 25 mmol cyclohexanone (or cyclohexene or KA oil), magnetic agitation is at 60 ~ 90 ℃ of reaction 3 ~ 12 h down; After reaction finished, in 0 ℃ of following standing over night, separated out a large amount of white crystals in the reaction bulb this moment, is hexanedioic acid behind the liquid filtering.Weigh calculated yield;
The temperature sensitive type monomer comprises
N-alkyl acrylamide,
N-N-isopropylacrylamide,
N-n-pro-pyl acrylamide,
N, N-diethyl acrylamide,
N-tert-butyl group acrylamide,
N-NMA,
N-ethoxy acrylamide,
N-hydroxypropyl acrylamide can be in them one or more;
Cationic monomer comprise diallyldimethylammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac,
N, N-DMAA hydrochloride, polyacrylamide oxy-ethyl-trimethyl ammonium bromide, the methylacryoyloxyethyl trimethyl ammonium chloride,
N-(dimethylamino) methacryl amine hydrochlorate can be in them one or more;
Function monomer comprises acrylamide, DAAM, Methacrylamide, hydroxy-ethyl acrylate, hydroxypropyl acrylate, can be in them one or more;
Employed initator is water soluble starter, comprises ammonium persulfate, potassium peroxydisulfate, potassium peroxydisulfate-sodium hydrogensulfite or sodium sulfite, ammonium persulfate-sodium bisulfite or sodium sulfite;
Employed crosslinking agent is the compound with bi-vinyl, as
N, N '-methylene-bisacrylamide, two acrylic acid glycol ester;
Tungstenic compound is phosphotungstic acid, silico-tungstic acid, wolframic acid or sodium tungstate;
The used charge ratio of the present invention is: the temperature sensitive type monomer mass is the 32%-46% of monomer gross mass, preferred 48%; The function monomer quality is the 10%-30% of monomer gross mass, preferred 30%; Cationic monomer is the 20%-47% of monomer gross mass, preferred 24%; Initiator amount is 0.1% ~ 5% of monomer gross mass; Dosage of crosslinking agent is 0.01 ~ 0.1% of monomer gross mass.The synthetic reaction temperature of hydrogel is 20 ~ 60 ℃; Reaction time is 1 ~ 3 h;
Beneficial effect of the present invention:
This method is utilized the microreactor effect of hydrogel, and characteristics, synthetic two-phase catalyst such as structure is various.The result shows, the tungsten load amount height of this catalyst.This preparation method's cost is low, simple to operate, environmentally safe.Prepared catalyst structure is stable,, and Tungstenic compound is evenly distributed on the hydrogel grid, and the catalysis of pimelinketone synthesizing adipic acid is active high, and when less consumption, the yield of adipic acid can reach 80%.
Embodiment provided by the invention is as follows:
Following Example is to further specify of the present invention, rather than limits the scope of the invention.
Embodiment 1
Take by weighing 1.13 g(0.01mol) the temperature sensitive type monomer
N-N-isopropylacrylamide and 0.71 g(0.01mol) the cationic monomer diallyl alkyl dimethyl ammonium chloride solution of function monomer acrylamide (AM) and 0.9 g 60% is dissolved in the 5.5 ml water, stirs 0.5 h, adds the crosslinking agent that accounts for content of monomer 0.05%
N, N '-methylene-bisacrylamide and account for the initiator ammonium persulfate of content of monomer 1% after continue to stir 0.5 h, then this mixed solution is put into 50 ℃ water-bath reaction 3 h.48 h that after reaction finishes product at room temperature are soaked in water repeatedly change water to remove unreacted monomer and soluble polymer, and oven dry at last obtains xerogel.With certain density phosphotungstic acid (H
3PW
12O
40) solution soaks hydrogel continuous stirring 1 h at room temperature, leaves standstill 1 d then.Product repeatedly wash white solid, under 80 ℃, dry to constant weight, namely obtain hydrogel load phosphotungstic acid P (NIPAM-AM-DMDAAC)/HPW.
In 50 ml flasks, add a certain amount of catalyst, 11 ml 30%H
2O
2, 0.31 g oxalic acid, add the cyclohexanone of 25 mmol, magnetic agitation is heated to 90
oC, the reaction time is 11 h; After reaction finished, in 0 ℃ of following standing over night, separated out a large amount of white crystals in the reaction bulb this moment behind the liquid filtering.The yield of adipic acid can reach 56%.
Embodiment 2
With embodiment 1, cyclohexanone is changed to KA oil, the yield of adipic acid can reach 55%.
Embodiment 3
With embodiment 1, cyclohexanone is changed to cyclohexene, the hexanedioic acid synthesis reaction temperature is 80
oDuring C, the yield of adipic acid can reach 70%.
Embodiment 4
With embodiment 1, the cationic monomer diallyl alkyl dimethyl ammonium chloride is changed to acrylyl oxy-ethyl-trimethyl salmiac, and initiator ammonium persulfate is changed to ammonium persulfate-sodium bisulfite, adipic acid yield is 50%.
Embodiment 5
With embodiment 1, with the temperature sensitive type monomer
N-N-isopropylacrylamide is changed to
N-n-pro-pyl acrylamide, adipic acid yield is 50%.
Embodiment 6
With embodiment 1, the function monomer acrylamide is changed to DAAM, adipic acid yield is 52%.
Embodiment 7
With embodiment 1, phosphotungstic acid is changed to sodium tungstate and cyclohexanone is changed to KA oil, and the hexanedioic acid synthesising reacting time is 12h that the yield of adipic acid can reach 80%.
Embodiment 8
With embodiment 1, the cationic monomer diallyl alkyl dimethyl ammonium chloride is changed to acrylyl oxy-ethyl-trimethyl salmiac and diallyldimethylammonium chloride, the yield of adipic acid can reach 51%.
Embodiment 9
With embodiment 1, with the temperature sensitive type monomer
N-N-isopropylacrylamide is changed to
N-n-pro-pyl acrylamide and phosphotungstic acid is changed to silico-tungstic acid, the yield of adipic acid can reach 53%.
Embodiment 10
With embodiment 1, with the temperature sensitive type monomer
N-N-isopropylacrylamide is changed to
N-n-pro-pyl acrylamide and cyclohexanone is changed to cyclohexene, the hexanedioic acid synthesis reaction temperature is 80
oDuring C, the yield of adipic acid can reach 50%.
Claims (2)
1. temperature-sensitive hydrogel load tungsten catalyst and preparation method thereof the steps include:
(1) under the room temperature, takes by weighing temperature sensitive type monomer, cationic monomer and the function monomer of certain mass respectively, be dissolved in a certain amount of water under stirring and make certain density monomer solution;
(2) in above-mentioned solution, add a certain amount of initator and crosslinking agent, obtain mixed solution after the stirring;
(3) obtain product after above-mentioned mixed solution being placed the water-bath reaction certain hour of uniform temperature;
(4) above-mentioned product at room temperature is soaked in water 48 h repeatedly change water to remove unreacted monomer and soluble polymer, and oven dry at last obtains xerogel;
(5) soak a certain amount of xerogel with certain density Tungstenic compound solution, at room temperature continuous stirring a few hours, leave standstill 1d then.Product repeatedly wash white solid, under 80 ℃, dry to constant weight, namely obtain hydrogel load tungsten catalyst.
Employed wherein temperature sensitive type monomer comprises:
N-alkyl acrylamide,
N-N-isopropylacrylamide,
N-n-pro-pyl acrylamide,
N, N-diethyl acrylamide,
N-tert-butyl group acrylamide,
N-NMA,
N-ethoxy acrylamide,
N-hydroxypropyl acrylamide can be in them one or more.
Employed cationic monomer comprises: diallyldimethylammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac,
N, N-DMAA hydrochloride, polyacrylamide oxy-ethyl-trimethyl ammonium bromide, the methylacryoyloxyethyl trimethyl ammonium chloride,
N-(dimethylamino) methacryl amine hydrochlorate can be in them one or more.
Employed function monomer comprises: acrylamide, DAAM, Methacrylamide, hydroxy-ethyl acrylate, hydroxypropyl acrylate can be in them one or more.
Employed Tungstenic compound comprises: phosphotungstic acid, silico-tungstic acid, wolframic acid or sodium tungstate.
2. according to the preparation method of the described a kind of temperature-sensitive hydrogel load tungsten catalyst of claim 1, it is characterized in that used charge ratio is: the temperature sensitive type monomer mass is the 32%-46% of monomer gross mass; The function monomer quality is the 10%-30% of monomer gross mass; Cationic monomer is the 20%-47% of monomer gross mass; Initiator amount is 0.1% ~ 5% of monomer gross mass; Dosage of crosslinking agent is 0.01 ~ 0.1% of monomer gross mass.The synthetic reaction temperature of hydrogel is 20 ~ 60 ℃; Reaction time is 1 ~ 3 h.The synthetic reaction temperature of hexanedioic acid is 60 ~ 90 ℃; Reaction time is 3 ~ 12 h.
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| CN111471129A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Composition, preparation method and application of composition in catalyst carrier |
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| JP2021521272A (en) * | 2018-04-10 | 2021-08-26 | 江蘇揚農化工集団有限公司Ｊｉａｎｇｓｕ Ｙａｎｇｎｏｎｇ Ｃｈｅｍｉｃａｌ Ｇｒｏｕｐ Ｃｏ．，Ｌｔｄ． | Epichlorohydrin production process by direct epoxidation of chloropropene, modified heteropolymetalate-supported catalyst and production method |
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| CN109675626A (en) * | 2019-01-11 | 2019-04-26 | 南阳师范学院 | A kind of responsive to temperature type polyoxometallate composite catalyst and its synthetic method |
| CN109675626B (en) * | 2019-01-11 | 2021-12-28 | 南阳师范学院 | Temperature-sensitive polyoxometallate composite catalyst and synthesis method thereof |
| CN110563884A (en) * | 2019-04-10 | 2019-12-13 | 江苏扬农化工集团有限公司 | Preparation method of supported heteropolyacid catalyst |
| CN110563884B (en) * | 2019-04-10 | 2021-06-29 | 江苏扬农化工集团有限公司 | Preparation method of supported heteropolyacid catalyst |
| CN111471129A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Composition, preparation method and application of composition in catalyst carrier |
| CN111471192A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Preparation method and application of bismuth tungstate-graphene-conductive hydrogel |
| CN112625196A (en) * | 2020-11-01 | 2021-04-09 | 北京化工大学 | Preparation and application of ABA type block copolymer with reversible gel sol characteristic |
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